The invention provides surfactant systems and agricultural compositions that contain a surfactant system and one or more agriculturally active compounds. The surfactant systems may comprise alkyl polyglycosides, anionic surfactants, basic compounds, and/or nonionic surfactants. The surfactant systems and agricultural compositions exhibit excellent chemical and physical stability as well as tank-mix compatibility properties that are highly desirable for commercial products in the agricultural chemicals industry.
The challenge involved in developing commercially acceptable products containing agriculturally active compounds continues to increase due to the rapid emergence of more complex customer and regulatory requirements. The formulation of products containing multiple active ingredients with very different physical properties is increasingly required in the marketplace to provide a broader spectrum of biological activity in a single product offering. These agricultural compositions must exhibit excellent chemical stability and must also maintain a high level of physical stability under a severe range of storage and use conditions. Handling of a liquid product in bulk storage facilities represents a special challenge because the product can be subject to high shear forces at both high and low temperatures. The complexity of the application medium into which the compositions will be blended is also rapidly increasing, creating significant new requirements for compatibility in the application process. This emerging area of performance is critical to customer satisfaction and commercial success with a product since poor compatibility in the final use mixture can cause blockage of sprayer screens and nozzles, preventing proper application of the product. At the same time that the demand on the agrochemical composition performance has been increasing, the number of auxiliary chemicals approved for use in agrochemical compositions by the U.S. EPA has been decreasing due to more stringent standards for the toxicological and ecological properties of these materials.
There is a need in the art for new surfactant systems comprising combinations and applications of auxiliary chemicals which have both unique performance characteristics and a good environmental safety profile. The invention is directed to this, as well as other, important ends.
The invention provides surfactant systems comprising at least one alkyl polyglycoside; at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; at least one basic compound; and, optionally, at least one nonionic surfactant. The at least one anionic surfactant is preferably neutralized to the inflection point in the titration curve with the at least one basic compound. The surfactant systems may further comprise agriculturally active compounds and/or water.
The invention provides agricultural compositions comprising at least one agriculturally active compound; at least one alkyl polyglycoside; at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; at least one basic compound; and, optionally, at least one nonionic surfactant. The at least one anionic surfactant is preferably neutralized to the inflection point in the titration curve with the at least one basic compound. The agricultural compositions may further comprise water.
The invention provides flowable concentrates comprising water; at least one agriculturally active compound; at least one alkyl polyglycoside; at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; at least one basic compound; and, optionally, at least one nonionic surfactant. The at least one anionic surfactant is preferably neutralized to the inflection point in the titration curve with the at least one basic compound. The flowable concentrates may be, for example, suspoemulsions, aqueous suspension concentrates, aqueous emulsion concentrates, or oil-miscible flowable concentrates.
The invention provides water-in-oil emulsions, capsule emulsions and polymer-stabilized aqueous emulsions comprising water; at least one agriculturally active compound; at least one alkyl polyglycoside; at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; at least one basic compound; and, optionally, at least one nonionic surfactant. The at least one anionic surfactant is preferably neutralized to the inflection point in the titration curve with the at least one basic compound.
The surfactant systems, agricultural compositions, flowable concentrates, water-in-oil emulsions, capsule emulsions, and polymer-stabilized aqueous emulsions of the invention may further comprise other additives, such as thickeners, flow enhancers, wetting agents, antifoaming agents, buffers, lubricants, fillers, drift control agents, deposition enhancers, adjuvants, evaporation retardants, frost protecting agents, insect attracting odor agents, fragrances, and the like.
These and other aspects of the invention are described in more detail below.
It has been unexpectedly discovered that anionic surfactants neutralized with a basic component, plus an alkyl polyglycoside, and, optionally, a nonionic surfactant, result in surfactant systems that produce agricultural concentrates that exhibit good chemical and physical stability in normal storage conditions and also show good compatibility in a variety of tank mix conditions. Without intending to be bound by any theory of the invention, the surfactants act not only as stabilizers but may also provide an adjuvant effect for some of the agriculturally active compounds.
Any alkyl polyglycoside known in the art can be used in the invention. The alkyl polyglycoside of the invention may have formula (I):
R1O(R2O)b(Z)axe2x80x83xe2x80x83(I)
R1 is a monovalent organic radical having from about 6 to about 30 carbon atoms. R1 is preferably a C8-22 alkyl or alkenyl group, more preferably a C8-11 alkyl group. R2 is a divalent alkylene radical having from about 2 to about 4 carbon atoms. R2 is preferably ethylene or propylene, more preferably ethylene. b is 0 to about 100. b is preferably 0 to about 12, more preferably 0. Z is a saccharide residue having about 5 to about 6 carbon atoms. Z may be glucose, mannose, fructose, galasctose, talose, gulose, altrose, allose, apiose, gallose, idose, ribose, arabinose, xylose, lyxose, or a mixture thereof. Z is preferably glucose. a is an integer from 1 to about 6. a is preferably from 1 to about 3, more preferably about 2.
Preferred compounds of formula (I) are compounds of formula (II): 
where n is the degree of polymerization and is from 1 to 3, preferably 1 or 2, and R5 is a branched or straight chain alkyl group having from 4 to 18 carbon atoms or a mixture of alkyl groups having from 4 to 18 carbon atoms.
Exemplary alkyl polyglycosides include APG(copyright) 325 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 9 to 11 carbon atoms and has an average degree of polymerization of 1.6), PLANTAREN(copyright) 2000 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 8 to 16 carbon atoms and has an average degree of polymerization of 1.4), PLANTARN(copyright)) 1300 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 12 to 16 carbon atoms and has an average degree of polymerization of 1.6), AGRIMUL(copyright) PG 2067 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.7), AGRIMUL(copyright) PG 2069 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 9 to 11 carbon atoms and has an average degree of polymerization of 1.6), AGRIMUL(copyright) PG 2076 (Cognis Corporation, Cincinnati, Ohio) (an alkyl polyglycoside in which the alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.5), ATPLUS(copyright) 438 (Uniqema, Inc., Wilmington, Del.) (an alkylpolysaccharide in which the alkyl group contains 9 to 11 carbon atoms), and ATPLUS(copyright) 452 (Uniqema, Inc., Wilmington, Del.) (an alkylpolysaccharide in which the alkyl group contains 8 to 10 carbon atoms).
In preferred embodiments, the alkyl polyglycoside is a (C8-10 alkyl)-O(glucose)2 (e.g., AGRIMUL(copyright) PG 2067); a (C9-11 alkyl)-O(glucose)2 (e.g., AGRIMUL(copyright) PG 2069); or a mixture thereof.
The alkyl polyglycosides may be used in the compositions of the invention in an amount of about 0.1 to about 8% by weight, preferably in an amount of about 0.5 to 4% by weight.
The anionic surfactants used in the invention may be any known in the art. The anionic surfactants may be polyarylphenol polyalkoxyether sulfates and/or phosphates, C8-18 alcohol polyalkoxyether phosphates, carboxylates, and/or citrates, alkyl benzenesulfonic acids, and mixtures thereof.
In a preferred embodiment, the compositions of the invention comprise at least one polyarylphenol polyalkoxyether sulfate and/or at least one polyarylphenol polyalkoxyether phosphate.
In other embodiments, the compositions of the invention comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; and at least one anionic surfactant selected from C8-18 alcohol polyalkoxyether phosphates, C8-18 alcohol polyalkoxyether carboxylates, C8-18 alcohol polyalkoxyether citrates, and alkyl benzenesulfonic acids.
In other embodiments, the compositions of the invention comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; and at least one anionic surfactant selected from C8-18 alcohol polyalkoxyether phosphates and C8-18 alcohol polyalkoxyether citrates.
Exemplary polyarylphenol polyalkoxyether sulfates and phosphates include polyarylphenol polyethoxyether sulfates and phosphates, polyarylphenol polypropoxyether sulfates and phosphates, polyarylphenol poly(ethoxy/propoxy)ether sulfates and phosphates, and salts thereof. The term xe2x80x9carylxe2x80x9d includes, for example, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof. Exemplary polyarylphenol polyethoxyether sulfates and phosphates include distyrylphenol polyethoxyether sulfates and phosphates, and tristyrylphenol polyethoxyether sulfates and phosphates. The polyarylphenol polyalkoxether sulfates and phosphates may have a degree of alkoxylation (e.g., ethoxylation) of between about 1 and about 50, preferably between about 2 and about 40, more preferably between about 5 and about 30. Commercially available polyarylphenol polyalkoxyether sulfates and phosphates include, for example, SOPROPHOR(copyright) 4 D 384 (Rhodia Corporation, Cranbury, N.J.) (tristyrylphenol (EO)16 sulfate ammonium salt), SOPROPHOR(copyright) 3 D 33 (Rhodia Corporation, Cranbury, N.J.) (tristyrylphenol (EO)16 phosphate free acid), SOPROPHOR(copyright) FLK (Rhodia Corporation, Cranbury, N.J.) (tristyrylphenol (EO)16 phosphate potassium salt), DEHSCOFIX(copyright) 904 (Albright and Wilson Americas, Inc., Glen Allen, Va.) (tristyrylphenol polyethoxylated ether phosphate triethanolamine salt), HOE(copyright) S 3475 (Hoechst) (tristyrylphenol polyethoxylated ether phosphate triethanolamine salt), and SOPROPHOR(copyright) RAM/384 (tristyrylphenol polyethoxylated ether sulfate neutralized with polyethoxylated oleylamine). In other embodiments, the polyarylphenol polyalkoxyether sulfates and phosphates may be mono-arylphenol polyalkoxyether sulfates and phosphates, such as styrylphenol polyethoxyether sulfates and phosphates.
Exemplary C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates include STEPFAC(copyright) 8180 (Stepan Corporation, Northfield, Ill.) (tridecylalcohol (EO)3 phosphate), STEPFAC(copyright) 8181 (Stepan Corporation, Northfield, Ill.) (tridecylalcohol (EO)6 phosphate), STEPFAC(copyright) 8182 (Stepan Corporation, Northfield, Ill.) (tridecylalcohol (EO)12 phosphate), EMCOL(copyright) CN-6 (Cromptom Corporation, Greenwich, Conn.) (tridecylalcohol (EO)6 carboxylate), BIOSOFT(copyright) S100 (Stepan Corporation, Northfield, Ill.) (dodecylbenzene sulfonic acid), and WITCONATE(copyright) 1298 (Crompton Corporation, Greenwich, Conn.) (dodecylbenzene sulfonic acid). The C8-18 alcohol polyethoxyether phosphates, carboxylates and citrates may have a degree of ethoxylation of between about 1 and about 25, preferably between about 1 and about 20.
Other anionic surfactants may also be included in the agricultural compositions and surfactant systems of the invention. Such anionic surfactants include, for example, C8-20 alkyl carboxylates including fatty acids, C8-20 alcohol sulfates, C8-20 alcohol phosphate mono- and diesters, C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene ether carboxylates, sulfates and sulfonates, C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene phosphate mono- and diesters, C8-20 alkylbenzene sulfonates, naphthalene sulfonates and formaldehyde condensates thereof, lignosulfonates, C8-20 alkyl sulfosuccinates and sulfosuccinamates, and C8-20 acyl glutamates, sarcosinates, isethionates and taurates. Of these anionic surfactants, it is preferable to use C8-20 alkyl carboxylates including fatty acids, C8-20 alcohol sulfates, C8-20 alcohol phosphate mono- and diesters, C8-20 alcohol polyoxyethylene ether carboxylates, sulfates and sulfonates, C8-20 alcohol polyoxyethylene phosphate mono- and diesters, C8-20 alkylbenzene sulfonates, naphthalene sulfonates and formaldehyde condensates thereof, lignosulfonates, C8-20 alkyl sulfosuccinates and sulfosuccinamates, and C8-20 acyl glutamates, sarcosinates, isethionates and taurates.
In one embodiment, the compositions of the invention may comprise at least one anionic surfactant. In another embodiment, the compositions of the invention may comprise at least two anionic surfactants. In another embodiment, the compositions of the invention may comprise at least three anionic surfactants. In another embodiment, the compositions of the invention may comprise at least four anionic surfactants. The anionic surfactants may be used in the compositions in an amount of about 0.1 to about 8% by weight, preferably in an amount of about 1 to about 4% by weight.
The basic compounds may be any known in the art that are capable of neutralizing the anionic surfactants. Basic compounds include, for example, inorganic bases, C8-18 alkyl amine polyalkoxylates, alkanol amines, alkanol amides, and mixtures thereof.
Exemplary inorganic bases include ammonium hydroxides, sodium hydroxides, potassium hydroxides, calcium hydroxides, magnesium hydroxides, zinc hydroxides, and mixtures thereof. The C8-18 alkyl amine polyalkoxylates may be, for example, C8-18 alkyl amine polypropoxylates and/or C8-18 alkyl amine polyethoxylates. Exemplary C8-18 alkyl amine polyalkoxylates include tallow amine polyalkoxylates, cocoamine polyalkoxylates, oleylamine polyalkoxylates, and stearylamine polyalkoxylates. The C8-18 alkyl amine polyethoxyates may have from about 2 to about 50 moles of ethylene oxide per molecule, more preferably from about 2 to about 20 moles of ethylene oxide per molecule. Exemplary C8-18 alkyl amine polyethoxylates include tallow amine ethoxylates (2 moles EO or 8 moles EO), cocoamine ethoxylates, oleylamine ethoxylates, and stearylamine ethoxylates. Exemplary alkanol amines include diethanol amine and triethanol amine. Exemplary alkanol amides include oleic diethanolamide and linoleic diethanolamide, and the diethanolamides of other C8-18 fatty acids.
The basic compounds may be used in an amount of about 0.1 to 8% by weight, preferably in an amount of about 0.5 to 4% by weight.
The one or more anionic surfactants are preferably neutralized to the inflection point in the titration curve with the one or more basic compounds. One skilled in the art will recognize that the pH of the inflection will vary according to the acid and base strengths of the components being used, but will generally fall within the range of about pH 4 to about pH 9, preferably about pH 5 to about pH 7. For example, the compositions of the invention may comprise at least one polyarylphenol polyalkoxyether sulfate and/or at least one polyarylphenol polyalkoxyether phosphate neutralized to the inflection point in the titration curve with one or more basic compounds. In other embodiments, the compositions of the invention may comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates neutralized to the inflection point in the titration curve with one or more basic compounds; and at least one anionic surfactant selected from C8-18 alcohol polyalkoxyether phosphates, C8-18 alcohol polyalkoxyether carboxylates, C8-18 alcohol polyalkoxyether citrates, and alkyl benzenesulfonic acids neutralized to the inflection point in the titration curve with one or more basic compounds. The basic compound used to neutralize the different anionic surfactants may be the same or different. In other embodiments, the compositions of the invention may comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates neutralized to the inflection point in the titration curve with one or more basic compounds; and at least one anionic surfactant selected from C8-18 alcohol polyalkoxyether phosphates, and C8-18 alcohol polyalkoxyether citrates neutralized to the inflection point in the titration curve with one or more basic compounds. The basic compound used to neutralize the different anionic surfactants may be the same or different. In still other embodiments, the compositions of the invention comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates neutralized to the inflection point in the titration curve with one or more basic compounds; and at least one anionic surfactant selected from C8-18 alcohol polyalkoxyether carboxylates and alkyl benzenesulfonic acids neutralized to the inflection point in the titration curve with one or more basic compounds. The basic compound used to neutralize the different anionic surfactants may be the same or different.
In still other embodiments, the compositions of the invention comprise at least one anionic surfactant selected from polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates neutralized to the inflection point in the titration curve with one or more basic compounds; and one or more additional anionic surfactants neutralized to the inflection point in the titration curve with one or more basic compounds. The basic compound used to neutralize the different anionic surfactants may be the same or different. Such one or more additional anionic surfactants may include, for example, C8-20 alkyl carboxylates including fatty acids, C8-20 alcohol sulfates, C8-20 alcohol phosphate mono- and diesters, C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene ether carboxylates, sulfates and sulfonates, C8-20 alcohol and (C8-20 alkyl)phenol polyoxyethylene phosphate mono- and diesters, C8-20 alkylbenzene sulfonates, naphthalene sulfonates and formaldehyde condensates thereof, lignosulfonates, C8-20 alkyl sulfosuccinates and sulfosuccinamates, and C8-20 acyl glutamates, sarcosinates, isethionates and taurates. Of these one or more additional anionic surfactants, it is preferable to use C8-20 alkyl carboxylates including fatty acids, C8-20 alcohol sulfates, C8-20 alcohol phosphate mono- and diesters, C8-20 alcohol polyoxyethylene ether carboxylates, sulfates and sulfonates, C8-20 alcohol polyoxyethylene phosphate mono- and diesters, C8-20 alkylbenzene sulfonates, naphthalene sulfonates and formaldehyde condensates thereof, lignosulfonates, C8-20 alkyl sulfosuccinates and sulfosuccinamates, and C8-20 acyl glutamates, sarcosinates, isethionates and taurates.
The anionic surfactants and basic compounds are preferably used in a ratio of about 1:1. One basic compound may be used to neutralize one or more anionic surfactants. In other embodiments, more than one basic compound may be used to neutralize one or more anionic surfactants.
The surfactant systems of the invention may optionally further comprise one or more nonionic surfactants. The xe2x80x9cnonionic surfactantsxe2x80x9d are different compounds from the alkyl polyglycosides described herein. Exemplary nonionic surfactants include ethylene oxide-propylene oxide block copolymers, ethylene oxide-butylene oxide block copolymers, C2-6 alkyl adducts of ethylene oxide-propylene oxide block copolymers, C2-6 alkyl adducts of ethylene oxide-butylene oxide block copolymers, polypropylene glycols, polyethylene glycols, polyarylphenol polyethoxy ethers, polyalkylphenol polyethoxy ethers, polyglycol ether derivatives of saturated fatty acids, polyglycol ether derivatives of unsaturated fatty acids, polyglycol ether derivatives of aliphatic alcohols, polyglycol ether derivatives of cycloaliphatic alcohols, fatty acid esters of polyoxyethylene sorbitan, alkoxylated vegetable oils, alkoxylated acetylenic diols, and mixtures thereof. The ethylene oxide-propylene oxide block copolymers may comprise alkyl ether bases, such as butyl ether, methyl ether, propyl ether, ethyl ether, or mixtures thereof. Commercially available nonionic surfactants include, for example, TOXIMUL(copyright) 8320 (Stepan Corporation, Northfield, Ill.) (butyl ether derivative of EO/PO block copolymer) and WITCONOL(copyright) NS 500LQ (Crompton Corporation, Greenwich, Conn.) (butyl ether derivative of EO/PO block copolymer).
The nonionic surfactants may be used in an amount of 0 to about 8% by weight. In other embodiments, the nonionic surfactants may be used in an amount of more than 0 to about 8% by weight, preferably in an amount of about 0.1% by weight to about 8% by weight, more preferably in an amount of about 0.5% by weight to about 8% by weight, still more preferably in an amount of about 0.5% by weight to about 3% by weight.
The agriculturally active compound may be any known in the art. The term xe2x80x9cagriculturally activexe2x80x9d refers to chemicals and biological compositions, such as those described herein, which are effective in killing, preventing, or controlling the growth of undesirable pests, such as, plants, insects, mice, microorganism, algae, fungi, bacteria, and the like. These chemicals may commonly be known as, e.g., insecticides, miticides, bactericides, algaecides, fungicides, nematocides, herbicides and the like. The term may also apply to a compound that controls the growth of plants in a desired fashion (e.g., growth regulator), to a compound which mimics the natural systemic activated resistance response found in plant species (e.g., plant activator) or to a compound that reduces the phytotoxic response to a herbicide (e.g., safener).
Exemplary fungicides and bactericides include azoxystrobin, benalaxyl, benomyl, bitertanol, borax, bromocuonazole, sec-butylamine, captafol, captan, calcium polysulfide, carbendazim, chinomethionat, chlorothalonin, chlozolinate, copper sulfate, cyprodinil, cyproconazole, dichlofluanid, dichlorophen, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, diniconazole, dithianon, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin, fluazinam, fludioxonil, fluoroimide, fluqinconazole, flusulfamide, flutolanil, folpet, fosetyl, furalaxyl, guazatine, hexachlorobenzene, hexaconazole, hydroxyquinoline sulfate, inibenconazole, iminoctadine, ipconazole, iprodione, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxan, mepanipyrim, mepronil, mercuric chloride, metam, metalaxyl, metconazole, metiram, nabam, nickel bis(dimethyldithiocarbamate), nuarimol, oxadixil, oxine-copper, oxolinic acid, penconazole, pencycuron, phthalide, polyoxin B, procymidone, propamocarb, propiconazole, propineb, pyrifenox, pyroquilon, quintozene, sulfur, tebuconazole, tecloftalam, tecnazene, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trifloxystrobin, triforine, triticonazole, vinclozolin, zineb, ziram, and salts thereof, if appropriate.
Exemplary insecticides include abamectin, acephate, acrinathrin, amitraz, azadirachtin, azamethiphos, azinphos-methyl, azocyclotin, bensultap, bifenthrin, bromopropylate, buprofezin, butoxycarboxim, cartap, chlorfenapyr, chlorfenson, chlorfluazuron, clofentezine, coumaphos, cyfluthrin, beta-cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, theta-cypermethrin, cyromazine, DDT, deltamethrin, diafenthiuron, dicofol, dicrotophos, difenthiuron, diflubenzuron, emamectin benzoate, endosulfan, esfenvalerate, etoxazole, fenazaquin, fenbutatin oxide, fenoxycarb, fenpyroximate, fipronil, fluazuron, flucycloxuron, flufenoxuron, taufluvalinate, formetanate, furathiocarb, halofenozide, gamma-HCH, hexaflumuron, hexythiazox, hydramethylnon, hydrogen cyanide, lufenuron, methamidophos, methidathion, methiocarb, methomyl, methoxychlor, mevinphos, milbemectin, monocrotophos, nicotine, nitenpyram, novaluron, omethoate, organophosphorus compounds, oxamyl, oxydemeton-methyl, pentachlorophenol, phosphamidon, pymetrozin, permethrin, profenofos, pyridaben, resmethrin, rotenone, sulfluramid, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tetrachlorvinphos, tetradifon, tetramethrin, thiamethoxam, thiocyclam, thiodicarb, tralomethrin, trichlorfon, friflumuron, trimethacarb, vamidothion, and salts thereof, if appropriate.
Exemplary herbicides include acetochlor, acifluorfen, aclonifen, acrolein, alachlor, ametryne, amitrole, asulam, atrazine, benazolin, bensulfuron-methyl, bentazon, benzofenap, bialaphos, bifenox, bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil, chlomethoxyfen, chloramben, chloroacetic acid, chlorbromuron, chlorimuron-ethyl, chlorotoluron, chlomitrofen, chlorotoluron, chlorthal-dimethyl, clodinafop, clopyralid, clomeprop, cyanazine, 2,4-D, 2,4-DB, daimuron, dalapon, desmedipham, desmetryn, dicamba, dichlobenil, dichloroprop, diclofop, difenzoquat, diflufenican, dimefuron, dimethachlor, dimethametryn, dimethenamid, dinitramine, diquat, diuron, endothall, ethametsulfuron-methyl, fenac, fenclorim, fenoxaprop, fenoxaprop-ethyl, flamprop-methyl, flazasulfuron, fluazifop, fluazifop-p-butyl, flumetsulam, flumiclorac-penyl, fluoroglycofen, flumetsulam, flumeturon, flumioxazin, flupoxam, flupropanate, fluridone, flurtamone, fomasafen, fosamine, glufosinate, glyphosate, haloxyfop, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, isoproturon, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPB, mecoprop, mefenacet, mesotrione, metazachlor, methabenzthiazuron, methylarsonic acid, metolachlor, metobenzuron, naproanilide, naptalam, neburon, nonanoic acid, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, phenmedipham, picloram, pretilachlor, prodiamine, prometon, prometryn, propachlor, propazine, propisochlor, propyzamide, pyrazolynate, pyrazosulfuron-ethyl, pyributicarb, pyridate, quinclorac, quizalofop-ethyl, rimsulfuron, siduron, simazine, simetryn, sulfamic acid, 2,3,6-TBA, terbumeton, terbuthylazine, terbutryn, trichloroacetic acid, triclopyr, trietazine, thenylchlor, thiazopyr, tralkoxydim, trietazine, and salts thereof, if appropriate.
Exemplary growth regulators include 6-benzylaminopurine, chlormequat, chlorphonium, cimectacarb, clofencet, cloxyfonac, cyanamide, cyclanilide, daminozide, dikegulac, ethephon, flumetralin, forchlorfenuron, inabenfide, 2-(1-naphthyl)acetamide, mepiquat, paclobutrazol, N-phenylphthalamic acid, thidiazuron, uniconzole, and salts thereof, if appropriate.
Exemplary safeners include benoxacor, cloquintocet, dichlormid, fenclorim, fluxofenime, furilazole, oxabetrinil, and salts thereof, if appropriate.
Exemplary plant activators include acibenzolar-S-methyl, and salts thereof, if appropriate.
In the compositions of the invention, the agriculturally active compounds may be used singly or may be used in combinations of 2, 3, 4, 5, 6, 7 or more. For example, the compositions of the invention may comprise glyphosate; S-metolachlor; atrazine; glufosinate; acetochlor; mesotrione; glyphosate and S-metolachlor; glyphosate, S-metolachlor and atrazine; glyphosate, S-metolachlor, atrazine and benoxacor; S-metolachlor and atrazine; S-metolachlor, atrazine and benoxacor; S-metolachlor, atrazine and butavenacil; S-metolachlor, atrazine, benoxacor and butafenacil; glyphosate, acetochlor and atrazine; glyphosate, S-metolachlor and atrazine; glufosinate, acetochlor and atrazine; glufosinate, S-metolachlor and atrazine; mesotrione and S-metolachlor; mesotrione, S-metolachlor and benoxacor; mesotrione, S-metolachlor and atrazine; mesotrione, S-metolachlor, benoxacor and atrazine; glyphosate and flumioxazin; flumixoazin, glyphosate and flumiclorac; flumiclorac; or any other agriculturally active compounds singly or in combination.
The agriculturally active compounds may be present in the compositions of the invention in an amount of about 1 to about 75% by weight, preferably an amount of about 5 to about 70% by weight, more preferably in an amount of about 10 to about 65% by weight, still more preferably in an amount of about 10 to about 40% by weight. In other embodiments, the agriculturally active compounds may be present in the compositions of the invention in an amount of about 50 to about 65% by weight. It has been unexpectedly discovered that a broad range of agriculturally active compounds may be used in the compositions of the invention to provide stable compositions. For example, the agriculturally active compounds may be water-soluble, oil-soluble, or insoluble in water and oil. Thus, the compositions of the invention may contain agriculturally active compounds that are water-soluble, oil/solvent-soluble, and/or insoluble in water and oil/solvent. The agriculturally active compounds may be present in the compositions of the invention in the form of, for example, finely dispersed solids. In other embodiments, the agriculturally active compounds may be dispersed in a liquid phase.
The agricultural compositions and surfactant systems of the invention may further comprise other inert additives. Such additives include thickeners, flow enhancers, wetting agents, antifoaming agents, buffers, lubricants, fillers, drift control agents, deposition enhancers, adjuvants, evaporation retardants, frost protecting agents, insect attracting odor agents, UV protecting agents, fragrances, and the like. The thickener may be a compound that is soluble or able to swell in water, such as, for example, polysaccharides of xanthans (e.g., anionic heteropolysaccharides), alignates, guars or celluloses; synthetic macromolecules, such as polyethylene glycols, polyvinyl pyrrolidones, polyvinyl alcohols, polycarboxylates of swellable structure-forming silicates such as pyrogenic or precipitated silicic acids, bentonites, montmorillonites, hectonites, or attapulgites; or organic derivatives of aluminum silicates. The frost protecting agent may be, for example, ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol, urea, or mixtures thereof. The antifoaming agent may be, for example, a polydimethylsiloxane.
For water-based products, the surfactant systems of the invention may be made by combining water-soluble surfactants, water-soluble agriculturally active compounds, water-insoluble solid agriculturally active compounds and water. If a water-insoluble solid agriculturally active compound is present, milling a slurry of the agriculturally active compound, water, defoamer, and all or a portion of the water soluble surfactants may be indicated to achieve the desired particle size. The particle size may be an average particle size of about 1 to about 20 microns, preferably about 1 to about 15 microns, more preferably about 2 to about 10 microns.
For oil-based products, the surfactant systems of the invention may be made by combining the oil soluble surfactants with oily liquid agriculturally active compounds, oil miscible/oil soluble solvents, and oil insoluble solid agriculturally active compounds. If an oil insoluble solid agriculturally active compound is present, it may be necessary to mill a slurry of the agriculturally active compound, an oil or solvent, and a portion or all of the oil soluble surfactants to obtain the desired particle size. The particle size may be an average particle size of about 1 to about 20 microns, preferably about 1 to about 15 microns, more preferably about 2 to about 10 microns.
Methods for making the surfactant systems of the invention are also described in Examples 1-4.
It has also been unexpectedly discovered that the agricultural compositions and surfactant systems of the invention may be mixed with water to form stable suspoemulsions. For example, stable suspoemulsions will be formed in very soft water (i.e., water containing 0 ppm calcium carbonate equivalent) to very hard water (e.g., water containing over 2,000 ppm calcium carbonate equivalent). Suspoemulsions have a liquid aqueous phase, which is generally a continuous phase, a liquid oil phase, which is generally a discontinuous phase dispersed in the aqueous phase, and a solid particulate phase, which is a discontinuous phase dispersed in one or both of the liquid phases.
The surfactant systems and agricultural compositions of the invention may be used as flowable concentrates (which include suspoemulsions, aqueous suspension concentrates, aqueous emulsion concentrates, and oil miscible flowable concentrates), water-in-oil emulsions, capsule emulsions and polymer-stabilized emulsions. Flowable concentrates are often used for seed treatments.
It has also been unexpectedly discovered that the compositions of the invention may be mixed with fertilizers and maintain their stability. For example, when the compositions of the invention are mixed with fertilizers, they do not exhibit any visible flocculation after about one hour. The fertilizers may comprise, for example, nitrogen, phosphorous, and/or potassium. In one embodiment, the fertilizer may be 10-34-0 fertilizer.
The agricultural compositions and surfactant systems of the invention may be used in conventional agricultural methods. For example, the agricultural compositions and surfactant systems of the invention may be mixed with water and/or fertilizers and may be applied preemergence and/or postemergence to a desired locus by any means, such as airplane spray tanks, knapsack spray tanks, cattle dipping vats, farm equipment used in ground spraying (e.g., boom sprayers, hand sprayers), and the like. The desired locus may be soil, plants, and the like. The term xe2x80x9cplantsxe2x80x9d includes seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage and fruits.